Research progress and prospect of sodium halide solid-state electrolytes

doi:10.19799/j.cnki.2095-4239.2025.0167

Abstract

Abstract:

Developing novel solid-state electrolytes with excellent comprehensive performance is crucial for achieving high safety and high energy density in all-solid-state batteries. Among various electrolyte material systems, halide electrolytes have garnered widespread attention from academia and industry due to their high ionic conductivity, high oxidation potential, good ductility, and strong compatibility with cathode materials. While lithium-ion halide electrolytes have been extensively studied, sodium-ion halide electrolytes are still in their early developmental stages and face several challenges. Sodium halides exhibit differences in crystal structure, ion transport mechanisms, and electrochemical performance. A systematic understanding of their structure-property relationships is essential for guiding the development of high-performance electrolytes. This review summarizes recent advancements in sodium halide solid-state electrolytes, with particular emphasis on the influence of different crystal structures on sodium-ion transport mechanisms and the roles of defects, structural disorder, and polyanionic frameworks in enhancing ionic conductivity. The effects of various synthesis methods on the microstructure of these materials are also discussed. Furthermore, the interfacial stability, electrochemical stability window, and cycling performance of sodium halide electrolytes in all-solid-state batteries are systematically evaluated. Finally, this review outlines future development directions, aiming to advance sodium-ion halide electrolytes and promote next-generation energy storage technologies.

Key words: sodium halide solid electrolytes, ion transport mechanism, interface modification, solid-state battery

CLC Number:

TK 02

Yihua QIAN, Yaohong ZHAO, Qing WANG, Peng GUO, Dating PEI, Yirou ZENG. Research progress and prospect of sodium halide solid-state electrolytes[J]. Energy Storage Science and Technology, 2025, 14(9): 3389-3401.

Figures/Tables 7

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Table 1

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正极电解质	正极	隔层电解质	负极	初始库仑效率/%	比容量/mAh/g	容量保持率/%	Ref.
Na₂ZrCl₆	NaCrO₂	Na₃PS₄	Na-Sn	93.1	111(0.1C, 30 ℃)	—	[34]
Na_0.7La_0.7Zr_0.3Cl₄	NaCrO₂	Na₃PS₄	Na₂Sn	95.0	94(1C)	88 (0.3C, 70圈)	[22]
Na_2.25Y_0.25Zr_0.75Cl₆	NaCrO₂	Na₃PS₄	Na-Sn	97.1	—	89.3 (40 ℃, 1000圈)	[18]
NaAlCl₄	NaCrO₂	Na₃PS₄	Na₃Sn	94.0	112 (60 ℃, 1C)	82 (60 ℃, 1C, 500圈)	[29]
NaAlCl₄	NaNCM118	Na₃PS_3.85O_0.15	Na₃Sn	—	124(0.1C, 25 ℃)	—	[44]
NaTaCl₆	Na₃V₂(PO₄)₃	Na₃PS₄	Na₁₅Sn₄	99.6	111(0.1C)	95 (1C, 600圈)	[24]
0.5Na₂O₂-TaCl₅	Na_0.85Mn_0.5Ni_0.4Fe_0.1O₂	Na₃PS₄	Na₁₅Sn₄	—	106.3(0.1C)	66 (0.1C, 500圈)	[26]
Na₂O₂-HfCl₄	Na_0.85Mn_0.5Ni_0.4Fe_0.1O₂	Na₃PS₄	Na₁₅Sn₄	99.9	125.5(0.1C)	78 (0.1C, 700圈)	[27]